Facet-Controlled Synthesis of Platinum-Group-Metal Quaternary Alloys: The Case of Nanocubes and {100} Facets

Wang, Chenxiao; Huang, Zhennan; Ding, Y.; Xie, Minghao; Chi, Miaofang; Xia, Younan

doi:10.1021/jacs.2c12368

Cited by 31 publications

(13 citation statements)

References 35 publications

(73 reference statements)

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“…For dropwise injection, after the introduction of the first few drops, the instantaneous number (n t ) of Au(III) precursor ions in the reaction mixture will quickly reach a steady state. 23 Assuming that the reduction rate is independent of the initial precursor concentration, the consumption of the precursor from each drop can be derived separately. This means that n t can be expressed mathematically according to the following equation…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Twin Proliferation and Prolongation under Kinetic Control: Pd–Au Janus Icosahedra versus Pd@Au Core–Shell Starfishes

et al. 2023

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Heterogeneous bimetallic nanocrystals featuring explicit spatial configurations and abundant twin defects can simultaneously enable geometric and ligand effects to enhance catalytic and photonic applications. Herein, we report two growth patterns of Au atoms on penta-twinned Pd decahedra, involving twin proliferation to generate asymmetric Pd–Au Janus icosahedra and twin elongation to produce anisotropic Pd@Au core–shell starfishes, respectively. Mechanistic analysis indicates that the injection rate determines the lower-limit number (n low) of Au(III) ions in the steady state and thus controls the growth pattern. When n low ≤ 5.5, the kinetic rate is slow enough to initiate asymmetrical one-side growth but fast enough to outpace surface diffusion; Au tetrahedral subunits are successively proliferated along the axial ⟨110⟩ direction of Pd decahedra to form Pd–Au Janus icosahedra. Composed of five Pd and 15 Au tetrahedral subunits, such a heterogeneous icosahedron supports high (2.2 GPa) tensile strain and high strain difference up to +21.9%. In contrast, when n low > 5.5, the fast reduction kinetics promotes symmetric growth with inadequate surface diffusion. As such, Au atoms are laterally deposited along five high-indexed ⟨211⟩ ridges of Pd decahedra to generate concave Pd@Au core–shell starfishes with tunable sizes (28–40 nm), twin elongation ratios (33.82–162.08%), and lattice expansion ratios (8.82–20.10%).

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Twin Proliferation and Prolongation under Kinetic Control: Pd–Au Janus Icosahedra versus Pd@Au Core–Shell Starfishes

et al. 2023

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“…Among the common low-index crystal facets, the Pt cuboctahedron is mainly composed of (100) and (111) surfaces, whereas Pt cubes, octahedrons, decahedrons, and icosahedrons are mainly composed of (100) surfaces. Crystal faces of different orientations encircle the polyhedra (cubes, octahedrons, trioctahedrons, and tetrahedrons) − (Figures a and b). The coordination and atomic spacing of Pt are different with different crystal faces; therefore, the ORR activity is also changed.…”

Section: Pt/c Catalystsmentioning

confidence: 99%

Review and Perspectives of Carbon-Supported Platinum-Based Catalysts for Proton Exchange Membrane Fuel Cells

Yang

et al. 2023

Energy Fuels

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The proton exchange membrane fuel cell (PEMFC) is a fast growing nextgeneration energy conversion technology, which has broad application prospects in electric vehicles, such as portable power supplies, fixed power supplies, and the military industry. The development of PEMFCs has attracted much attention due to their high energy conversion efficiency, good low-temperature startup performance, no pollution, no noise, and other advantages. However, the cathodic oxygen reduction reaction (ORR) kinetics in fuel cells is slow. It is therefore necessary that we use a large number of carbon-supported platinum (Pt)based catalysts in order to speed up the reaction. As a result, the current problems of high cost and low durability of carbon-supported Pt-based catalysts have become a major reason for limiting the successful commercialization of fuel cells. To meet the requirements of high catalytic activity and high stability of carbon-supported Pt-based catalysts, this review summarizes the research progress and methods for optimizing the performance of carbonsupported Pt-based catalysts for PEMFCs. In addition, this review highlights the current progress in improving the performance of carbon-supported Pt-based catalysts in terms of the reduction of particle size, exposure of highly active crystal surfaces, control of Pt particle morphology, and preparation of Pt−M alloys as well as some support characteristics and preparation technologies. Furthermore, the development of carbon-supported Pt-based catalysts in the direction of fuel cells and the main challenges they will face in practical applications are also proposed in this review. In summary, the carbonsupported Pt-based catalysts optimized using the above methods show great potential in the ORR. With continuous improvement of preparation and characterization technologies, carbon-supported Pt-based catalysts have broad applications and market prospects.

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“…Recently, various strategies such as wetchemical synthesis and thermal shock synthesis are shown to obtain size reduction of HEA nanoparticles below 10 nm, which can achieve impressively high mass activities toward various gasphase thermocatalysis and liquid-phase electrocatalysis (Table S1). Despite the extensive use of HEA nanocatalysts, it has been very difficult to further improve the specific activity by maneuvering the types of facets exposed on the surface through facet engineering [20][21][22][23][24][25][26][27][28][29][30][31] . Tailoring exposed facets of HEA nanocatalysts accordingly introduces a wide scope of binding energies for the reactants, intermediates, and/or products, bringing more opportunities for enhancing catalytic performance.…”

Section: Mainmentioning

confidence: 99%

A Library of High-Entropy-Alloy Nanocrystals with Controlled Surface Atomic Arrangements for Catalysis

Yang

Hsiao

et al. 2023

Preprint

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High-entropy-alloy (HEA) nanocrystals consisting of a minimum of five elements have recently emerged as a versatile family of catalysts due to immense chemical space and tunability1-3. However, there are no effective strategies for synthesizing libraries of HEA nanocrystals with controlled surface atomic structures of exposed facets for boosting catalytic performance4-19. Due to the distinct nucleation and growth kinetics of constituent metals and their distinctive crystal structures, it is incredibly challenging to confine five or more different metal species situated on the nanocrystal surface with a specific arrangement but also in a high-entropy random mixing state. Here we present a straightforward strategy to craft a library of facet-controlled HEA nanocrystals with up to ten dissimilar metallic elements (Pt, Pd, Ir, Ru, Rh, Os, Au, Fe, Co, and Ni) by solution-phase layer-by-layer epitaxial growth, enabling the design of 638 distinct catalysts with 5 to 10 elements in equimolar ratios. The subnanometer-thick solid-solution HEA atomic layers can be deposited epitaxially on nanocrystal seeds with {100} and {111} facets, thus achieving HEA shells with square and hexagonal atomic arrangements, respectively. The hollow HEA nanocages with ultrathin walls along a specific direction can be further fabricated via post-synthetic chemical etching. Three facet-dependent catalytic actives of HEA nanocrystals are discovered in electrocatalysis and photocatalysis, and their catalytic facets with real active sites are also identified by in situ synchrotron X-ray absorption spectroscopy and density-functional theory calculations. Our work enables facet engineering in the multi-elemental space and unveils the critical needs for their future development toward catalysis.

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Facet-Controlled Synthesis of Platinum-Group-Metal Quaternary Alloys: The Case of Nanocubes and {100} Facets

Cited by 31 publications

References 35 publications

Twin Proliferation and Prolongation under Kinetic Control: Pd–Au Janus Icosahedra versus Pd@Au Core–Shell Starfishes

Twin Proliferation and Prolongation under Kinetic Control: Pd–Au Janus Icosahedra versus Pd@Au Core–Shell Starfishes

Review and Perspectives of Carbon-Supported Platinum-Based Catalysts for Proton Exchange Membrane Fuel Cells

A Library of High-Entropy-Alloy Nanocrystals with Controlled Surface Atomic Arrangements for Catalysis

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